3,3,7,11-Tetramethyltricyclo[
6
.3.
0
.
0
^<2,
4
>]undecane skeleton is found in a number of natural products, which are divided into two groups, aromadendranes (I) and alloaromadendranes (II). Recently, some coupled compounds with other organic moieties were found,
e
.g., macrocarpals (3), which were exhibiting HIV-RTase inhibitory activities. We planned to develop a general synthetic route to these compounds. We selected 7-substituted tricyclo[
6
.3.
0
.
0
^2,
4
>]undecenone derivatives (
4
) as common key intermediates for both groups, I and II. Both nuclei would be obtained by control in the stereochemistry of the reduction of
C
-8-
C
-
9
double bond. (+)-3-Carene (
5
) was converted to a cyclic β-keto ester 8 in a
5
-step sequence.
4
-Methyl derivatives (10 and 11) and
4
-CH_2OTBDMS derivatives (12 and 13) were synthesized from 8. Compound 10 was converted to a tricyclic enone (
4
a) by allylation at
C
-2, the Wacker oxidation followed by the aldol ring closing reaction. Similarly, the enone
4
b
was obtained from 12. Stereoselective introduction of a methyl group at
C
-11 of
4
was accomplished to afford 18 and
22
selectively. Deoxygenation of 18 gave (+)-1,2-didehydroaromadendrane (24). Catalytic hydrogenation of
22
afforded a
B
/
C
-trans compound 25 preferentially. The Birch reduction of
22
also produced only 25. Compound 25 was converted to (+)-aromadendrene (1) by reduction of the ketone, esterification with PTC-Cl, radical reductive deoxygenation, deprotection of TBDMS, mesylation followed by elimination with DBU. (-)-Alloaromadendrene (2) was obtained from
22
by an intramolecular-type hydrogen migration occurring in the reduction of the tosylhydrazone with a hydride as a crucial step.
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